Illustrated Physics
physics, drawn
Concept

Vapour pressure — where it appears

The pressure of a substance's vapour in equilibrium with its liquid or solid at a given temperature. It rises steeply with temperature, sets the boiling point where it equals the surrounding pressure, and is lowered over the concave liquid surfaces in narrow pores.

Named by 8 essays across 2 fields — each of them below, with the objects they name alongside it.

A siphon's pressure, and the 10.09 m it cannot pass. The absolute pressure of the liquid along a siphon, from the upper surface, over the crown, and down to an outlet 1.2 m below the surface, for 4 crown heights. The profile is hydrostatic and depends on nothing but height: the tube's shape, its length and its bore do not appear. At the crown the liquid is below atmospheric pressure by ρg times the lift, and the whole question of how high a siphon can reach is whether that number stays above the liquid's vapour pressure — 2.34 kPa for water at 20 °C, which puts the ceiling at 10.09 m. a 2 m crown sits at 81.7 kPa and holds, a 6 m crown sits at 42.5 kPa and holds, a 9.5 m crown sits at 8.1 kPa and holds, a 11.5 m crown sits at -11.5 kPa and is below the vapour pressure, so it boils. The ceiling is a property of the liquid, not of the mechanism: a degassed liquid that can be pulled into tension has no such limit, and siphons in a vacuum.

The height a siphon cannot pass

A siphon will not lift water more than about ten metres, and the usual explanation for the limit is also given as the explanation for the mechanism. It cannot be both. A siphon runs in a vacuum, with degassed water, over a crown no atmosphere could support.

fluids · Hydrostatics The pore size the air decides. The largest pore radius that holds condensed water in equilibrium with air at a given relative humidity, for water at 25 °C, on a logarithmic radius axis. A concave meniscus lowers the vapour pressure over it by exp(−2γVₘ/rRT), so a pore whose meniscus would be tighter than a radius set by the humidity is in equilibrium only when full. The upper curve is the emptying condition, through a hemispherical meniscus with two curvatures; the lower is the filling condition, through the cylindrical film that lines a pore before it closes, with one — so the same pore fills at a higher humidity than it empties at. At 50% humidity a pore empties below 1.51 nm and fills below 0.76 nm; at 90% humidity a pore empties below 9.96 nm and fills below 4.98 nm; at 99% humidity a pore empties below 104 nm and fills below 52 nm. The radii run from molecular at low humidity to a tenth of a micrometre at 99 per cent, and every one was checked by putting it back into the vapour-pressure relation.

The pore that fills from dry air

Water condenses when the air is saturated — on a flat surface. Over a curved one the vapour pressure is different, higher over a drop and lower over a meniscus, and in a pore a few nanometres across it is low enough that the pore fills with liquid from air at half humidity. The water it holds is under a tension of a hundred megapascals, and the pore empties at a lower humidity than it filled at, for a reason that needs no roughness at all.

fluids · Capillarity How supersaturated a cloud is, to an ice crystal. The supersaturation over ice of air that is just saturated over liquid water, eᵥᵥ/eᵢ − 1, in per cent, against temperature; dashed, the same computed from the chemical potentials, exp(LΔT/RT·Tₘ) − 1, with L the latent heat of melting per mole, ΔT the supercooling and Tₘ the melting point. A supercooled cloud is in balance with its droplets, so to any ice crystal inside it the air is 5.1 per cent supersaturated at −5 °C, 10.5 at −10, 22.0 at −20 and 41.2 at −35. Over the droplets themselves it is exactly saturated, so they neither grow nor shrink by vapour. The excess is the chemical-potential difference between supercooled water and ice, 217 J per mole at −10 °C, expressed as a pressure ratio.

The ice that grows by stealing from the droplets

Most clouds colder than freezing are not made of ice. They are made of droplets of liquid water, some tens of degrees below their freezing point, waiting for something to start them freezing. When a few ice crystals do appear among them, the crystals grow and the droplets shrink, without touching, because supercooled water has a higher chemical potential than ice and so a higher vapour pressure: air balanced with the droplets is ten per cent supersaturated, to an ice crystal, at minus ten degrees. A few crystals among a hundred thousand droplets each take everything, grow heavy enough to fall, and that is how most of the rain outside the tropics begins — as snow.

thermodynamics · Chemical potential The distance at which the air takes over. Evaporation of water at 20 °C into dry air, in kilograms per square metre per second, against the thickness of the layer the vapour must cross before it is carried away, both on logarithmic scales, with the kinetic and diffusive resistances added in series: 1/u + δ/D, where u = √(RT/2πM) is the speed at which the kinetic flux carries vapour off and D the diffusion coefficient. Dashed, the kinetic ceiling. At one atmosphere the two resistances are equal at δ = D/u = 0.17 μm, about two and a half mean free paths of the air; a layer much thinner than that leaves the surface at its ceiling, and a layer much thicker throttles it in proportion to its thickness. At a tenth of an atmosphere diffusion is ten times faster and the crossover moves out to 1.7 μm. Only in vacuum, or across gaps shorter than a mean free path, does the liquid itself set the rate.

The puddle that could dry in a second

A liquid in equilibrium with its vapour loses molecules exactly as fast as the vapour delivers them, and kinetic theory says how fast that is. For water at room temperature it is two and a half kilograms per square metre every second — a puddle two and a half millimetres deep gone in a second. Puddles take hours because almost every molecule that leaves is knocked back by the air within a fraction of a micrometre. The ceiling binds only where the vapour can escape in a single free flight: in vacuum, where water freezes itself, in the smallest droplets, and on the filament of a lamp.

thermodynamics · Kinetic theory Latent heat of boiling against boiling point. The heat needed to boil one mole of a liquid at its normal boiling point, against that boiling point, both on logarithmic axes, for twenty-one substances from helium to sodium. The line is ΔH = 87.2 J/(mol K) × Tb, the mean entropy of boiling of the ordinary liquids boiling between 250 and 700 K, which scatter about it by 3.3 per cent; the ordinary liquids as a whole (blue), from neon at 27 K to sodium at 1,156 K, by 10.0 per cent, the coldest lying low. Water, ammonia and the alcohols (red) need more heat than the line predicts, acetic acid (green) less; the quantum liquids helium and hydrogen (violet) fall far below.

The entropy every liquid gains on boiling

Divide the heat it takes to boil a liquid by the temperature at which it boils, and for benzene, chloroform, acetone, hexane, ether and carbon tetrachloride the answer comes out within a few per cent of the same number — about ten and a half times the gas constant. Frederick Trouton noticed it in 1884. It is a statement about entropy, and once it is read that way the liquids it fails for become the interesting ones: water and the alcohols, whose hydrogen bonds hold the liquid in order; acetic acid, whose vapour is made of pairs; and helium, whose liquid is already as disordered as quantum mechanics allows.

thermodynamics · Phase change The boiling point in a column of water, and the depth heating reaches it first. The temperature at which water boils against depth in a geyser's conduit 2240 m above sea level, where the air's pressure is 77.6 kPa (solid): 92.7 °C at the surface, 103.6 °C at 4 m, 115.5 °C at 10 m and 131.8 °C at 22 m — rising steeply near the top and more gently below, because each extra metre adds the same pressure to water whose boiling point responds less as it gets hotter. Dashed: the water as it heats from beneath, cooled to 80 °C at the top by the pool and below that warming by only 0.8 °C per metre, mixed by convection; 6 °C and 3 °C short of the curve at 4 m, and then touching it. It touches at 4 m, not at the bottom: there the water is still 13.7 °C below boiling.

The column that boils from the middle

Water at the bottom of a geyser's tube is hotter than water anywhere else in it, and it is not the water that boils first. The weight of the column raises the boiling point with depth faster than the heat from below raises the temperature, so the column reaches its boiling curve partway down, under a cooler surface layer. A little boiling there lifts the water above. Everything beneath is then at a lower pressure than the one it was heated under, so it is superheated and flashes, and the eruption feeds itself: past about fourteen centimetres of water thrown out, each slug of steam makes more room than it was given.

thermodynamics · Phase change Newcomen's dilemma. Two consequences of how cold a Newcomen engine's injection spray leaves its cylinder, against that temperature: the pressure difference the atmosphere then pushes the piston down with, one atmosphere less the vapour pressure of the water left in the cylinder; and the steam the next stroke wastes reheating the cylinder's iron skin, as a fraction of the most it wastes at 30 °C (8.2 cylinder-fulls). A cylinder cooled to 40 °C gives a push of 0.93 atmospheres and wastes 7.0 cylinder-fulls of steam a stroke; one left at 70 °C wastes half as much but pushes with only 0.69. Every choice was bad, because the one vessel had to be both hot, to receive the steam, and cold, to make the vacuum. Newcomen's engineers ran it in between.

The cylinder that must not be cooled

The first steam engines that did useful work, Thomas Newcomen's pumps of 1712, made a vacuum by spraying cold water into a cylinder full of steam. It worked, and on every stroke it cooled the cylinder, so that the next charge of steam condensed on the cold iron until the walls were hot again — several cylinders' worth of steam spent heating metal that the next spray would cool. James Watt saw in 1765 that the vessel was being asked to be hot and cold at once, and moved the cold to a separate condenser. The improvement was a factor of three or four in coal. A century later the reason had a name: heat passing from hot to cold across a large difference, doing nothing on the way, is work thrown away.

thermodynamics · Heat engines The pipe that out-conducts any solid. The temperature difference needed to carry 30 W along a rod 300 mm long and 6 mm across, on a logarithmic scale: for solid aluminium 1343 K, for copper 796 K, for diamond, the best conductor of heat at room temperature, 159 K; and for a water heat pipe of the same size 0.8 K, almost all of it across the thin wet wicks where the heat goes in and comes out. Solid metal could not do it at all: the hot end of the copper rod would have to be hundreds of degrees above the cold. The heat pipe carries the heat as latent heat in moving vapour, and the vapour needs almost no temperature difference to flow. As an effective conductivity that is 1000 times copper's — which is why every laptop and many satellites move their heat in pipes rather than through metal.

The pipe that carries heat as vapour

A copper rod six millimetres across and thirty centimetres long, asked to carry thirty watts from a laptop's processor to its fan, would need its hot end eight hundred degrees above its cold end. The flattened copper tube that actually does the job manages it with less than a degree. It is a heat pipe: sealed, emptied of air, and holding a few drops of water and their vapour. The water boils at the hot end, the vapour rushes to the cold end and condenses, and a wick of sintered copper powder drags the liquid back by capillarity. The heat goes as latent heat, and vapour needs almost no temperature difference to flow — which makes the pipe a thousand times better than copper, as long as its wick can keep up.

thermodynamics · Phase change

Named alongside it

The objects these essays reach for when they reach for this one.

Latent heatChemical potentialClausius clapeyronBoiling pointCapillarityCavitationSurface tensionAtmospheric pressureBergeron processBoundary conditionsCapillary condensationCapillary pressure

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